JP2007023246A - New silicon-containing compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new compound that is a silicon-containing compound containing an amino group or an amide group in the same molecule, has a long carbon chain length to bond nitrogen to silicon and contains an aromatic group or a heteroaromatic group as a third functional group at the side chain and to provide a method for producing the same. <P>SOLUTION: The silicon-containing compound is represented by general formula (1) [A and X are each independently hydrogen, a 1-18C acyclic hydrocarbon group which may be substituted or a polymerizable group selected from a (meth)acryloyl group, an aryl group, a propargyl group, a (meth)acrylic acid hydroxyalkyl group, a (meth)acrylic acid alkyl group and the like; Ar is a group selected from an aryl group, an alkoxycarbonyl group, a silyl group and a vinyl group; n is an integer of 3-10; X<SB>1</SB>, X<SB>2</SB>and X<SB>3</SB>are each independently a methyl group, a trimethylsiloxy group or an organosiloxy group containing ≤18 silicon atoms]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel silicon-containing compound. More specifically, the present invention relates to a silicon-containing compound having an amino group or an amide group in the same molecule, more preferably an aromatic group or a heteroaromatic group, and a method for producing the same.

  A siloxane bond (Si-O) has a long bond distance and a low electron density, so that the bond can be easily rotated. That is, it can be said that it is more flexible than the CC chain and is flexible. In the case of a typical dimethylpolysiloxane chain, two methyl groups are bonded to a silicon atom, which is bulky and vibrates with a relatively large amplitude, so that adjacent molecules are difficult to approach. That is, the intermolecular distance is large, the intermolecular force is low, the surface tension is small, and the orientation is exhibited depending on the nature of the contacting surface. These properties have wide application as antifoaming agents, mold release agents, water repellents, softeners, various coating materials and the like. In addition, it has good gas and water vapor permeability due to its three-dimensional structure, and is used for medical and clothing materials (Reference: Silicone Handbook, edited by Kunio Ito, Nikkan Kogyo Shimbun, 1990).

  On the other hand, the nitrogen atom of an amino group or an amide group has polarity due to the presence of an unpaired electron that does not participate in a covalent bond, and has high affinity with water, which is a polar solvent, and other functional groups such as a cyano group and High reactivity with carboxyl group, hydroxyl group and the like. Therefore, polymers having such groups are adhesives, surface hydrophilization of metals, plastics, glass, etc., hydrophilic film formation and anti-fogging treatment agents, improved hygroscopicity of textile products, hair cosmetics, films for manicure, etc. It is used as a forming substance or as a biosensor by using it as an ion selective electrode.

  In recent years, a silicon-containing compound having an amino group or an amide group has been developed as a substance having both of the above physical properties, and particularly used as ophthalmic lens materials such as contact lenses and intraocular lenses as medical materials (US Pat. 711, 943, JP-A-3-15019, JP-A-11-326848, JP 2003-522227, etc.). These promote the supply of oxygen to the cornea when used as a contact lens, for example, for the purpose of moderate water wettability, transparency as an optical material, biocompatibility, lipid stain resistance, etc. In order to express the oxygen permeability, transparency, biocompatibility of the contained compound, the hydrophilicity of the amide group, and the lipid stain resistance, both are used as monomers in one compound. .

  By the way, when using a compound having both of the above physical properties, it is possible to use a monomer having each group in an appropriate ratio without using a monomer having both groups in one compound. There is also an idea that it should be. However, as described above, the silicon-containing monomer has high water repellency and has a problem in compatibility with the polar amide group or amino group-containing monomer, and the blending ratio is naturally limited. Moreover, in order to make both compatible, since a uniform mixed system cannot be obtained unless other monomers or organic solvents are used, originally desired characteristics are deteriorated, and it is difficult to obtain a transparent material. There was a problem of becoming.

  Accordingly, silicon-containing compounds as disclosed in the above publications have been proposed. In the compounds presented in these publications, in order to express the characteristics of each functional group more clearly, it is better to have a certain distance between the two functional groups. It is desirable in the sense that it is not easily affected.

  However, each of the above publications discloses a compound in which an amide group (nitrogen in it) and a siloxane group (silicon in it) are bonded via an alkylene having 1 to 10 carbon atoms. The structures specifically disclosed in the description are only examples of compounds in which the number of carbon atoms between nitrogen and silicon is limited to 3 (propylene). There is no document specifically disclosed. The reason for this is not clear, but the most likely reason is that it is not possible to synthesize compounds via other carbon numbers on a commercial scale.

  Furthermore, if other functional groups other than the above, particularly aromatic groups and heteroaromatic groups can be contained in the molecular structure, it is expected that the possibility of obtaining a compound with a wider application range is increased. .

  US Pat. No. 4,711,943   Japanese Patent Laid-Open No. 3-15019   Japanese Patent Laid-Open No. 11-326848   Special table 2003-522227 gazette

  The object of the present invention has been made in view of the above prior art, and is a silicon-containing compound having an amino group or an amide group in the same molecule, wherein the carbon chain length connecting nitrogen and silicon is long, and Is to provide a novel compound having an aromatic group or heteroaromatic group in the side chain as a third functional group, and a method for producing the same.

  And in this invention, as a result of earnestly examining in order to solve the said subject, by making 3-chloropropyl trisiloxysilane etc. react with a thioamide dianion, the silicon-containing compound which has the target amino group is obtained. We found that synthesis is possible. Further, the present inventors have found that various substituents can be bonded via an amide bond by reacting the amino group with, for example, a carboxyl group-containing compound, thereby completing the present invention.

  That is, the present invention relates to the general formula (1):

（式中、Ａ及びＸは、それぞれ独立に、水素、炭素数１〜１８の置換されていてもよい非環式炭化水素基、
（メタ）アクリロイル基、アリル基、プロパルギル基、（メタ）アクリル酸ヒドロキシアルキル基、（メタ）アクリル酸アルキル基などから選択される重合性基、
Ａｒはアリール基、アルコキシカルボニル基、シリル基、ビニル基、から選択される基、
ｎは３〜１０の整数であり、
Ｘ_１、Ｘ_２、Ｘ_３はそれぞれ独立にメチル基、トリメチルシロキシ基、Ｓｉ原子が１８個以下のオルガノシロキシ基を示す）で表されるシリコン含有化合物およびその製造方法に関する。

(In the formula, A and X each independently represent hydrogen, an optionally substituted acyclic hydrocarbon group having 1 to 18 carbon atoms,
A polymerizable group selected from a (meth) acryloyl group, an allyl group, a propargyl group, a hydroxyalkyl group (meth) acrylate, an alkyl (meth) acrylate group, and the like;
Ar is a group selected from an aryl group, an alkoxycarbonyl group, a silyl group, and a vinyl group,
n is an integer of 3 to 10,
X ₁ , X ₂ , and X ₃ each relate to a silicon-containing compound represented by a methyl group, a trimethylsiloxy group, and an organosiloxy group having 18 or less Si atoms) and a method for producing the same.

  Since the silicon-containing compound of the present invention has a primary or secondary amino group in the molecular structure, the structure can be modified by various reactions such as condensation with an acid chloride, acylation, alkylation, and the like. It can be used as a polymerizable monomer by introduction. For example, when the polymerizable monomer is used as a material for a medical device (for example, an ophthalmic lens such as a contact lens or an intraocular lens), it has excellent oxygen permeability due to siloxane in the molecular structure and a bonding group derived from an amino group. It can be expected to improve hydrophilicity and biocompatibility. In addition, the presence of an aromatic group or heteroaromatic group, which is the third functional group contained in the structure of the compound, enables a wider range of molecular designs by introducing various substituents into the group. did. Furthermore, the condensate obtained by the reaction of the amino group in the compound of the present invention with another isocyanate compound is a curable resin composition suitable for applications such as adhesives such as glass, resin and metal, sealants and primers. Can be used as

Hereinafter, the compound of the present invention and the production method thereof will be described in more detail.
The compound of the present invention has the general formula (1):

（式中、Ａ及びＸは、それぞれ独立に、水素、炭素数１〜１８の置換されていてもよい非環式炭化水素基、
（メタ）アクリロイル基、アリル基、プロパルギル基、（メタ）アクリル酸ヒドロキシアルキル基、（メタ）アクリル酸アルキル基などから選択される重合性基、
Ａｒはアリール基、アルコキシカルボニル基、シリル基、ビニル基、から選択される基、
ｎは３〜１０の整数であり、
Ｘ_１、Ｘ_２、Ｘ_３はそれぞれ独立にメチル基、トリメチルシロキシ基、Ｓｉ原子が１８個以下のオルガノシロキシ基を示す）で表されるシリコン含有化合物である。

(In the formula, A and X each independently represent hydrogen, an optionally substituted acyclic hydrocarbon group having 1 to 18 carbon atoms,
A polymerizable group selected from a (meth) acryloyl group, an allyl group, a propargyl group, a hydroxyalkyl group (meth) acrylate, an alkyl (meth) acrylate group, and the like;
Ar is a group selected from an aryl group, an alkoxycarbonyl group, a silyl group, and a vinyl group,
n is an integer of 3 to 10,
X ₁ , X ₂ and X ₃ are each a silicon-containing compound represented by a methyl group, a trimethylsiloxy group, or an organosiloxy group having 18 or less Si atoms.

  Specific examples of the optionally substituted acyclic hydrocarbon group having 1 to 18 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, Linear alkyl groups such as n-octyl and n-decyl, branched alkyl groups such as isopropyl, isobutyl, t-butyl, acyl groups such as acetyl, propionyl, butyryl, pivalyl, lauroyl, myristoyl, cyclopropylmethyl group, cyclohexylmethyl Groups, hydroxy-substituted alkyl groups such as hydroxymethyl and 2-hydroxyethyl, halogen-substituted alkyl groups such as trifluoromethyl, trifluoroethyl and hexafluoroisopropyl, as well as alkoxy groups such as methyleneoxy, ethyleneoxy and propyleneoxy, Benzylmethyl, toluylmethi An arylmethyl group such as a Kishirirumechiru, pyridylmethyl, furylmethyl, heterocyclic hydrocarbon group such as thio-furylmethyl and the like. The term “acyclic” means that an aromatic ring, a heteroaromatic ring, a cyclohydrocarbon ring structure, or the like is not directly bonded, and an aromatic ring, a heteroaromatic ring, a cyclohexane via an alkylene group. The thing to which a hydrocarbon ring structure couple | bonds is meant to include. Of these, a branched alkyl group and an arylmethyl group are preferred because they are easily synthesized.

X ₁ , X ₂ , and X ₃ in the formula (1) each independently have 18 Si atoms such as methyl, trimethylsiloxy, pentamethyldisiloxy, methylbis (trimethylsiloxy) siloxy, and tris (pentamethylsiloxy) siloxy. Or less organosiloxy groups. Of these, a trimethylsiloxy group is preferable because it is easily available.

  Ar in the formula (1) is preferably an aryl group, for example, a 1 to 3 membered aromatic hydrocarbon such as phenyl, toluyl, xylyl, biphenyl, naphthyl, anthracenyl, etc. In addition, alkoxycarbonyl is used to enhance hydrophilicity. It may have a substituent such as a silyl group for improving oxygen permeability and a vinyl group for improving polymerizability.

  Here, it is desirable to include an aromatic ring structure, which is one of the characteristics of the compound of the present invention, in any one of A, X, and Ar. It is easy to introduce various substituents into the aromatic ring structure. If various substituents are introduced as a post-treatment after forming a material using the compound of the present invention, a material with higher functionality can be obtained. This is because it can also be designed.

  As an example, the compound of the present invention can be synthesized via a starting material (thioamide) by the following reactions.

  The reaction formula (a) is a compound useful as a raw material of the present invention, and R is selected from a branched or cyclic alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group, an aryl group, and a heteroaromatic group. Group. Examples of such branched alkyl groups include isopropyl, isobutyl, t-butyl, etc., cyclic alkyl groups such as cyclopropyl and cyclohexyl, aryl groups such as benzyl, toluyl and xylyl, and heteroaromatic groups such as pyridyl. , Furyl, thioflyl and the like. These are due to the high yield in generating the next reaction, thioamide dianion.

  Ar in the reaction formula (a) is the same as described above.

  In this reaction, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, toluene or the like can be used as an organic solvent. Of these, dimethylformamide is preferred from the viewpoint of easy separation of the product in the process of washing with water after the reaction.

  Moreover, this reaction is performed at 60-110 degreeC, Preferably it is 80-90 degreeC. When the temperature is lower than the above temperature, the reaction rate decreases and the target product cannot be obtained in a high yield. When the temperature is higher, side reactions are likely to occur, and purification takes time.

  The above reaction can be carried out in a molar ratio range of aldehyde group-containing compound: sulfur: amino group-containing compound = 1: 1: 1 to 1: 1.2: 1.2. Among these ratios, the most preferable ratio is 1: 1.1: 1.1, because the aldehyde group-containing compound is completely consumed, and the purification of the subsequent product can proceed efficiently. This reaction is called a Willgercddt-Kindler reaction and is described in detail in the literature (Brown, EV Synthesis 1975, 358).

  The starting material (thioamide) is obtained as described above, and the silicon-containing compound of the present invention can be obtained by the following reaction.

なお、この反応の最終生成物の窒素に結合するＲＣＨ_２をＡとし、同窒素に結合する水素については、そのまま用いるか、あるいは種々の置換反応により置換させてＸとしたものが、本願発明のシリコン含有化合物である。前記置換反応の例としては、（メタ）アクリル酸クロリドを反応させてシリコン含有化合物をモノマー化する、あるいは（メタ）アクリロイル基を有するエポキシドやオキセタンを同窒素に結合した水素により開環させることによってもモノマー化することができる。

In this connection, RCH ₂ bonded to nitrogen of the final product of this reaction is A, and hydrogen bonded to the nitrogen is used as it is or is replaced by X by various substitution reactions. It is a silicon-containing compound. Examples of the substitution reaction include reacting (meth) acrylic acid chloride to monomerize a silicon-containing compound, or by opening a ring of epoxide or oxetane having a (meth) acryloyl group with hydrogen bonded to the same nitrogen. Can also be monomerized.

  Among the above reactions, the upper reaction generates a dianion, specifically, a reaction disclosed in the literature (Murai, T. et al., J. Org. Chem. 2003, 68, 8514). is there. A point to note at the start of the reaction is that it must be carried out under nitrogen or argon atmosphere under dehydrating conditions. Otherwise, the thioamide dianion cannot exist stably and may be easily decomposed by the presence of water or oxygen. Of course, other organolithium reactants can be used, but nBuLi is most preferable because it is the cheapest and can be easily separated from the reaction system as butane gas.

  Tetrahydrofuran (THF) is used as the exemplified reaction solvent. As other solvents, toluene, diethyl ether and the like can be used, but the former may cause a slight side reaction, and the latter precipitates without dissolving the reaction intermediate and lowers the reaction yield. In some cases, the most preferred is THF. The reaction temperature can be carried out in the range of −78 ° C. to room temperature, but about 0 ° C. is appropriate considering the side reaction and efficiency.

  The mixing ratio of each compound to be reacted is not generally determined depending on the compound to be used, but generally, about 2 equivalents of nBuLi is added to thioamide, and then about 1.1 equivalents of silicon-containing halide is added. To do. When the equivalent amount of nBuLi is small, the generation efficiency of dianion is lowered, and when the silicon-containing halide is large, side reaction products are increased, and purification is troublesome.

  Next, by the lower reaction, the thioamide bond is reduced to a secondary amine bond. The solvent used for this reaction can be used as long as it is an alcohol solvent, and the reaction proceeds at a temperature around room temperature. Note that if this temperature is high, the reaction of cleaving the nitrogen-carbon bond on the opposite side may proceed, so care must be taken. In order to obtain a primary amine, a hydrogenation reaction using a Pd catalyst by a reaction described later can be used.

  The compound thus obtained is characterized by having the above-mentioned three types (amino group, aryl group, siloxane group) functional group. Among these, as described above, the siloxane portion is excellent in transparency and oxygen permeability, while having high water repellency, while imparting hydrophilicity by the amino group or other group that reacts with the amino group. By appropriately adding a hydrophilic group or an alkyl group to the aryl group, the structure can be modified into a compound having multiple functions. Taking advantage of these characteristics, this compound can be used, for example, as an antifoaming agent, a cleaning agent, a dispersing agent, a release agent, an adhesive, an antifogging agent, a coating additive, a resin modifier, and a medical device. Can also be used.

  In addition, since the compound of the present invention has an aromatic hydrocarbon in the side chain, it has a high refractive index and has an ultraviolet absorption effect. Therefore, it is a surface coating agent such as glass, resin, metal, fiber treatment agent, silicone modified rubber. It can be used for materials.

  Furthermore, the compound of the present invention can be structurally modified by using an amine having a halogen-substituted aryl group in the reaction formula (a), and the hardness of the resulting resin when used as a monomer in a polymerization reaction Can be adjusted in various ways. In addition, by synthesizing the silicon-containing compound of the present invention and then introducing an alkylamino group into the aryl group, the hydrophilicity of the hydrophobic aryl group can be improved. Furthermore, by introducing a perfluoroalkyl group as an oxygen inhalation functional group, it is possible to coexist oxygen affinity, oxygen inhalation property, hydrophilic property, and hydrophobic function group in the same molecule.

  In order to clarify the present invention more specifically, several examples according to the present invention are illustrated below.

  According to the reaction formula shown below, silicon-containing compound 4 (N-phenylmethyl N-1- (3- (tris (trimethylsiloxy) silylpropyl) phenylmethylamine) and silicon-containing compound 5 (N-phenylmethyl N- 1- (3- (Tris (trimethylsiloxy) silylpropyl) phenylmethylpropenamide) can be obtained.

−化合物２（Ｎ−フェニルメチルベンゼンカルボチオアミド）の合成−
ベンジルアミン（１２．０ｍＬ，０．１１ｍｏｌ）のジメチルホルムアミド（ＤＭＦ）（５０ｍＬ）溶液にベンズアルデヒド（１０．１ｍＬ，０．１ｍｏｌ）を室温で加えた。ついで硫黄（３．５２ｇ，０．１１ｍｏｌ）を加え８０〜９０℃で６時間撹拌しながら加熱した。反応混合液をエチルエーテル（５０ＭＬ）に注ぎ、有機層を飽和炭酸水素ナトリウム水溶液（２００ｍＬ）、塩酸（３５％，１０ｍＬ）で洗浄を行った。有機層を硫酸マグネシウムで乾燥させ、ろ過、減圧濃縮を行った。残渣をヘキサン／塩化メチレン（１：１，３０ｍＬ）で再結晶し、化合物２を黄色固体として２１．３ｇ（収率：９４％）を得た。

-Synthesis of Compound 2 (N-phenylmethylbenzenecarbothioamide)-
Benzaldehyde (10.1 mL, 0.1 mol) was added to a solution of benzylamine (12.0 mL, 0.11 mol) in dimethylformamide (DMF) (50 mL) at room temperature. Subsequently, sulfur (3.52 g, 0.11 mol) was added and heated at 80 to 90 ° C. with stirring for 6 hours. The reaction mixture was poured into ethyl ether (50 ML), and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution (200 mL) and hydrochloric acid (35%, 10 mL). The organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was recrystallized from hexane / methylene chloride (1: 1, 30 mL) to obtain 21.3 g (yield: 94%) of Compound 2 as a yellow solid.

-Synthesis of compound 3 by introduction of siloxanyl group-
Compound 2 (1.82 g, 8.0 mmol) was dissolved in THF (16 mL). N-Butyllithium-hexane solution (13 mL, 16 mmol) was gradually added to this solution at 0 ° C. After stirring for 30 minutes, 1-chloro-3-tristrimethylsiloxaneoxypropane (3.56 mL, 8.8 mmol) was added at the same temperature and stirring was continued for another 30 minutes. Water (approximately 10 mL) was added to the reaction mixture, and the organic layer was extracted with diethyl ether (approximately 20 mL). The collected organic layer was washed twice with water (about 10 mL), and the aqueous layer was re-extracted with diethyl ether (about 10 mL). The collected organic layer was dried over magnesium sulfate. The reaction mixture was filtered and concentrated, and the resulting residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 8) to give 3.8 g of Compound 3 as a yellow solid (yield: 84%). Obtained.

¹ H- nuclear magnetic resonance spectrum and ¹³ C- nuclear magnetic resonance spectrum of Compound 3 using a JEOL JNMα-400 model, in deuterated chloroform, 25 ° ^C., 1 H- nuclear magnetic resonance spectrum 8 cumulative The ¹³ C-nuclear magnetic resonance spectrum was measured with 128 integrations.
The results are as follows.
¹ H NMR (CDCl ₃ ) δ-0.015 (s, 27 H, CH ₃ ), 0.48 (m, 2 H, CH ₂ ), 1.38 (m, 2 H, CH ₂ ), 1.96 (m , 1H, CH ₂ ), 2.10 (m, 1H, CH ₂ ), 5.69 (q, 1H, J = 8 Hz, CH), 7.2-7.4 (m, 8H, C ₆ H ₅ ), 7.64 (m, 2H, C ₆ H ₅ ).
¹³ C NMR (CDCl ₃ ) δ1.8, 14.2, 20.2, 38.9, 59.7, 126.7, 127.0, 127.8, 128.5, 128.9, 131.0 140.6, 142.4, 198.3.

-Synthesis of silicon-containing compound 4 by reduction reaction of compound 3-
Compound 3 (4.51 g, 8.0 mmol) was dissolved in THF (16 mL). Thereto, lithium aluminum hydride (1.22 g, 32.35 mmol) was slowly added at 0 ° C. Wait until the foam was almost gone, then THF was refluxed for 2 hours. The reaction mixture was brought to 0 ° C. again, and water (1.22 mL), 15% aqueous sodium hydroxide solution (1.22 mL), and water (3.66 mL) were slowly added. The reaction mixture was filtered to obtain 3.61 g (yield: 85%) of the corresponding compound 4 as a yellow oil.

The ¹ H-nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum of Compound 4 are as follows.
¹ H NMR (CDCl ₃ ) δ 0.0 (s, 27 H, CH ₃ ), 0.35 (m, 2 H, CH ₂ ), 1.1-1.3 (m, 2 H, CH ₂ ), 1.6 −1.8 (m, 2H, CH ₂ ), 3.49 (d, 1H, J = 13.2 Hz, CH ₂ ), 3.56 (t, 1H, J = 6.8 Hz, CH), 3. _{61 (d, 1H, J =} 13.2Hz, CH 2), 7.15-7.3 (m, 10H, C 6 H 5).
¹³ C NMR (CDCl ₃ ) δ 1.8, 14.4, 20.3, 41.9, 51.6, 62.5, 126.8, 126.9, 127.4, 128.2, 128.33 128.35, 140.9, 144.4.

-Synthesis of silicon-containing compound 5 by acryloylation of compound 4-
Compound 4 (3.34 g, 7.0 mmol) was dissolved in methylene chloride (20 mL), and 4-dimethylaminopyridine (0.065 g, 0.53 mmol) and triethylamine (1.47 mL, 7.0 mmol) were added at 0 ° C. More acryloyl chloride (0.74 mL, 7.0 mmol) was added slowly. After stirring at 0 ° C. for 10 minutes, the mixture was stirred at room temperature for 15 hours. Dilute hydrochloric acid (1N, about 3 mL) was added to the reaction mixture. The reaction mixture was divided into an aqueous layer and an organic layer, and the aqueous layer was extracted with methylene chloride (about 10 mL). The combined organic layers were washed twice with dilute hydrochloric acid (about 5 mL) and saturated aqueous sodium chloride solution (about 10 mL). Furthermore, the operation of extraction from the aqueous layer was repeated twice. The combined organic layers were dried with magnesium sulfate. The reaction mixture was filtered and concentrated, and the resulting residue was purified by silica gel column chromatography (ethyl acetate: hexane = 5: 1) to give 3.7 g of Compound 5 as a yellowish white oil (yield: 89%). )

The ¹ H-nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum of Compound 5 are as follows.
¹ H NMR (CDCl ₃ ) δ 0 (s, 27 H, CH ₃ ), 0.38 (m, 2 H, CH ₂ ), 1,25 (m, 2 H, CH ₂ ), 1.80 (m, 1 H, CH ₂ ), 1.90 (m, 1H, CH ₂ ), 4.45 (m, 2H, CH ₂ ), 5.55 (m, 1H, ═CH ₂ ), 5.96 (m, 1H, ═CH _{2), 6.38 (m, 2H} , = CH.CH), 6.94 (m, 2H, C 6 H 5), 7.16-7.4 (m, 8H, C 6 H 5)
¹³ C NMR (CDCl ₃ ) δ 1.7, 14.2, 20.6, 34.1, 47.1, 56.7, 126.1, 126.7, 127.6, 127.7, 128.2 , 128.4, 128.7, 138.3, 139.6, 167.1
In the nuclear magnetic resonance spectrum, a signal based on a conformer was also observed. Ratio between isomers = 74: 26

  Synthesis of Compound 6 ((1-Phenyl) -4- (Tris (trimethylsiloxy) silylbutylamine) by Hydrogenation of Compound 4 (Formula 5)

化合物４（１．０７ｇ，２．０ｍｍｏｌ）をメタノール（１２ｍＬ）に溶かし、ついで水酸化パラジウム（０．３２８ｇ，２．０ｍｍｏｌ）を加えた。フラスコ内を水素置換し、室温で四日間撹拌を行った。反応混合液をセライトでろ過し、濃縮することで化合物６（０．７４ｇ，８３％）を高純度で得た。

Compound 4 (1.07 g, 2.0 mmol) was dissolved in methanol (12 mL), and then palladium hydroxide (0.328 g, 2.0 mmol) was added. The flask was replaced with hydrogen and stirred at room temperature for 4 days. The reaction mixture was filtered through celite and concentrated to give compound 6 (0.74 g, 83%) with high purity.

The ¹ H-nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum of Compound 6 are as follows.
¹ H NMR (CDCl ₃ ) δ 0 (s, 27 H, CH ₃ ), 0.38 (m, 2 H, CH ₂ ), 1.17 (m, 1 H, CH ₂ ), 1.25 (m, 1 H, CH ₂ ), 1.63 (m, 2H, CH ₂ ), 2.10 (brs, 2H, NH ₂ ), 3.83 (t, J = 7.2 Hz, 1H), 7.1-7.3 ( m, 5H, C ₆ H ₅ )
¹³ C NMR (CDCl ₃ ) δ1.7, 14.3, 20.4, 42.9, 56, 1,126.4, 127.0, 128.5, 146.1

  Synthesis of N-1-phenylmethyl 1-methylpropanethioamide 2b (Formula 6)

ベンジルアミン（０．８７ｍＬ，７．９ｍｍｏｌ）のジメチルホルムアミド（ＤＭＦ）（８ｍＬ）溶液にイソブチルアルデヒド（０．７２ｍＬ，７．９ｍｍｏｌ）を室温で加えた。ついで硫黄（０．２５９ｇ，８ｍｍｏｌ）を加え８０−９０℃で３時間撹拌しながら加熱した。反応混合液をエーテル（１０ｍＬ）に注ぎ、有機層を飽和炭酸水素ナトリウム水溶液（２０ｍＬ）、塩酸（３５％，３ｍＬ）で洗浄を行った。有機層を硫酸マグネシウムで乾燥させ、ろ過、減圧濃縮を行った。残渣をヘキサン／エーテル（およそ１０：１，１０ｍＬ）で再結晶し、Ｎ−１−フェニルメチル１−メチルプロパンチオアミド２ｂを白色固体として１．１３ｇ（収率：７４％）得た。
^１Ｈ ＮＭＲ（ＣＤＣｌ_３）δ１．０６（ｄ，Ｊ＝６．９０Ｈｚ，６Ｈ，ＣＨ_３），２．６９（ｍ，Ｊ＝６．９０，１Ｈ，ＣＨ），４．６０（ｄ，Ｊ＝４．９Ｈｚ，２Ｈ，ＣＨ_２），７．２−７．４（ｍ，５Ｈ，Ｃ_６Ｈ_５）．
^１３Ｃ ＮＭＲ（ＣＤＣｌ_３）δ２２．６，４４．４，４９．９，１２８．１，１２８．２，１２９．０，１３６．２，２１１．６．

To a solution of benzylamine (0.87 mL, 7.9 mmol) in dimethylformamide (DMF) (8 mL) was added isobutyraldehyde (0.72 mL, 7.9 mmol) at room temperature. Subsequently, sulfur (0.259 g, 8 mmol) was added and heated at 80-90 ° C. with stirring for 3 hours. The reaction mixture was poured into ether (10 mL), and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution (20 mL) and hydrochloric acid (35%, 3 mL). The organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was recrystallized from hexane / ether (approximately 10: 1, 10 mL) to obtain 1.13 g (yield: 74%) of N-1-phenylmethyl 1-methylpropanethioamide 2b as a white solid.
¹ H NMR (CDCl ₃ ) δ 1.06 (d, J = 6.90 Hz, 6H, CH ₃ ), 2.69 (m, J = 6.90, 1H, CH), 4.60 (d, J = _{4.9Hz, 2H, CH 2),} 7.2-7.4 (m, 5H, C 6 H 5).
¹³ C NMR (CDCl ₃ ) δ 22.6, 44.4, 49.9, 128.1, 128.2, 129.0, 136.2, 211.6.

Synthesis of N-1-phenyl-4- (tris (trimethylsiloxy) silylbutyl 1-methylpropanthioamide 3b (Formula 7)
Thioamide 2b (0,97 g, 5.0 mmol) was dissolved in THF (5 mL). An n-butyllithium-hexane solution (7.5 mL, 12 mmol) was gradually added thereto at 0 ° C. After stirring for 30 minutes, 1-chloro-3-tris (trimethylsiloxy) silylpropane (2.2 mL, 5.5 mmol) was added at the same temperature and stirring was continued for another 30 minutes. Water (approximately 10 mL) was added to the reaction mixture and the organic layer was extracted with ether (approximately 20 mL). The collected organic layers were washed twice with water (approximately 10 mL) and the aqueous layer was re-extracted with ether (approximately 10 mL). The collected organic layer was dried over magnesium sulfate. The reaction mixture was filtered and concentrated, and the resulting residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 20) to obtain 0.351 g (yield: 13%) of compound 3b as a white solid. Got.
¹ H NMR (CDCl ₃ ) δ 0.05 (s, 27 H, CH ₃ ), 0.55 (m, 2 H, CH ₂ ), 1.20 (d, J = 7.0 Hz, 6 H, CH ₃ ), 1 .75 (m, 2H, CH ₂ ), 2.55 (t, J = 7.0 Hz, 2H, CH ₂ ), 2.68 (m, 1H, CH), 6.10 (m, 1H, CH) _{, 7.2-7.4 (m, 5H, C} 6 H 5).
¹³ C NMR (CDCl ₃ ) δ 1.8, 14.4, 17.9, 18.2, 40.8, 43.4, 62.5, 126.8, 127.6, 128.8, 140.7 , 210.3.

Synthesis of N-1-phenyl-4- (tris (trimethylsiloxy) silyl) butyl N-1-methylpropylamine 4b (Formula 8)
Compound 3b (0.35 g, 0.66 mmol) was dissolved in THF (1.4 mL). Thereto was slowly added lithium aluminum hydride (0.1 g, 2.64 mmol) at 0 ° C. Wait until the foam was almost gone, then THF was refluxed for 2 hours. The reaction mixture was again brought to 0 ° C., and water (0.102 mL), 15% aqueous sodium hydroxide solution (0.102 ml), and water (0.306 mL) were slowly added. The reaction mixture was filtered to obtain 0.286 g (yield: 87%) of the corresponding amine 4b as a yellow oil.
¹ H NMR (CDCl ₃ ) δ 0.21 (s, 27H, CH ₃ ), 0.58 (m, 2H, CH ₂ ), 1.02 (d, J = 7.0 Hz, 6H, CH ₃ ), 1 _{.3-1.5 (m, 2H, CH 2} ), 1.7-1.9 (m, 3H, CH, CH 2), 2.3-2.5 (m, 2H, CH 2), 3 .70 (t, 1H, J = 6.8Hz, CH), 7.28-7.5 (m, 5H, C 6 H 5).
¹³ C NMR (CDCl ₃ ) δ 1.8, 14.4, 20.3, 20.7, 20.82.8.5, 42.0, 55.8, 63.4, 126.7, 127.2 , 128.2, 144.9.

Synthesis of Amide 5b by Acryloylation of Amine 4b (Formula 9)
Amine 4b (1.135 g, 2.27 mmol) was dissolved in methylene chloride (9 mL), and 4-dimethylaminopyridine (0.021 g, 0.00017 mmol) and triethylamine (0.475 mL, 3.4 mmol) were added at 0 ° C. In addition, more acryloyl chloride (0.24 mL, 2.95 mmol) was added slowly. After stirring at 0 ° C. for 10 minutes, the mixture was stirred at room temperature for 12 hours. Dilute hydrochloric acid (1N, approximately 2 mL) was added to the reaction mixture. The reaction mixture was divided into an aqueous layer and an organic layer, and the aqueous layer was extracted with methylene chloride (approximately 10 mL). The combined organic layers were washed twice with dilute hydrochloric acid (approximately 5 mL) and saturated aqueous sodium chloride solution (approximately 10 mL). Furthermore, the operation of extraction from the aqueous layer was repeated twice. The combined organic layers were dried with magnesium sulfate. The reaction mixture was filtered and concentrated, and the resulting residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 30), and 0.736 g (yield: 59%) of Compound 5b as a pale yellow oil. )
¹ H NMR (CDCl ₃ ) δ 0.05 (s, 27H, CH ₃ ), 0.45 (t, J = 6.8 Hz, 2H, CH ₂ ), 0.60 (d, J = 6.8 Hz, 3H) _{, CH 3), 0.75 (brs} , 3H, CH 3), 1.35-1.45 (m, 2H, CH 2), 1.5 (m, 1H, CH), 1.90-2. _{10 (m, 2H, CH 2} ), 2.9-3.0 (m, 2H, CH 2), 5.62 (m, 1H, = CH 2), 5.7 (m, 1H, CH), _{6.3 (m, 1H, = CH} 2), 6.5 (m, 1H, = CH), 7.1-7.3 (m, 5H, C 6 H 5).
In the nuclear magnetic resonance spectrum, signals based on conformers were also observed. Ratio between isomers = 61: 39.

N-1-phenylmethyl, N-3-methacryloxy-2-hydroxypropyl 1-phenyl-4- (tris (trimethylsiloxy)) silylbutylamine 7 and N-1-phenylmethyl, N-1-hydroxymethyl-2- Synthesis of methacryloxyethyl 1-phenyl-4- (tris (trimethylsiloxy)) silylbutylamine 7 ′ (formula 10)
Add amine 4 (1.068 g, 2 mmol) to acetonitrile (6 mL), then add glycidyl methacrylate (0.546 mL, 4 mmol), calcium triflate (Ca (OTf) ₂ , 0.338 g, 1 mmol), 60-65 Stirring was carried out at 7 ° C for 7 hours. The reaction mixture was concentrated and washed twice with methylene chloride (approximately 10 mL). The organic layer was dried with magnesium sulfate. The reaction mixture was filtered and concentrated, and the resulting residue was purified by silica gel column chromatography (ethyl acetate: hexane: triethylamine = 17: 82: 1), and compounds 7 and 7 ′ were combined as a pale yellow oil. 0.592 g (yield: 43%) was obtained.

-Polymerization of contact lens material using Compound 7-
After adding and dissolving 0.5 part of 2,2′-azobisisobutyronitrile as a polymerization initiator to 100 parts by weight of Compound 7, two glass plates (75 mm × 25 mm × 2 mm) The solution was poured into a jig sandwiched between a nylon sheet and a silicone spacer with a thickness of 0.2 mm hollowed to φ15.
Next, the jig is stopped with a clip so as not to leak, and the temperature is raised from room temperature to 60 ° C. in 1 hour in a programmed temperature rising oven, kept at the same temperature for 2 hours, and then to 90 ° C. in 1 hour. The temperature was raised and held at that temperature for 2 hours. Further, the temperature was raised to 110 ° C. over 1 hour, heated at the same temperature for 2 hours, and then gradually cooled to room temperature to obtain a film-like polymer having a thickness of 0.2 mm. The resulting film was transparent and hard.

-Polymerization of hydrous contact lens material using Compound 7-
To a mixture of 30 parts of Compound 7, 70 parts of N, N-dimethylacrylamide and 0.3 part of ethylene glycol dimethacrylate, 0.3 part of 2,2′-azobisisobutyronitrile as a polymerization initiator is added and dissolved. After that, the solution was poured into the jig used above and the polymerization operation was performed under the same conditions as described above to obtain a film-like polymer having a thickness of 0.2 mm.
When the obtained film was immersed in purified water for about 2 hours, it was a transparent and flexible film.

Claims (4)

A silicon-containing compound represented by the general formula (1).

(In the formula, A and X each independently represent hydrogen, an optionally substituted acyclic hydrocarbon group having 1 to 18 carbon atoms,
A polymerizable group selected from a (meth) acryloyl group, an allyl group, a propargyl group, a hydroxyalkyl group (meth) acrylate, an alkyl (meth) acrylate group, and the like;
Ar is a group selected from an aryl group, an alkoxycarbonyl group, a silyl group, and a vinyl group,
n is an integer of 3 to 10,
X ₁ , X ₂ and X ₃ each independently represent a methyl group, a trimethylsiloxy group, or an organosiloxy group having 18 or less Si atoms)   The compound represented by the general formula (1), wherein A is a hydroxyalkyl group (meth) acrylate, X is hydrogen or an arylmethyl group, and n = 3. 2. The silicon-containing compound according to 1.   2. The silicon-containing compound according to claim 1, wherein the compound is represented by the general formula (1), wherein A and X are hydrogen and n = 3. The method of synthesizing the silicon-containing compound according to claim 1, wherein the thioamide represented by the general formula (2) is dianionized with n-butyllithium and then reacted with a terminal halogen organosiloxane.

Wherein R is a group selected from a branched or cyclic alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group, an aryl group, and a heteroaromatic group;
Ar is a group selected from an aryl group, an alkoxycarbonyl group, a silyl group, and a vinyl group)